CN102741985B - Aqueous dispersion for chemical mechanical polishing and utilize its chemical and mechanical grinding method - Google Patents
Aqueous dispersion for chemical mechanical polishing and utilize its chemical and mechanical grinding method Download PDFInfo
- Publication number
- CN102741985B CN102741985B CN201180007853.2A CN201180007853A CN102741985B CN 102741985 B CN102741985 B CN 102741985B CN 201180007853 A CN201180007853 A CN 201180007853A CN 102741985 B CN102741985 B CN 102741985B
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- China
- Prior art keywords
- aqueous dispersion
- mechanical polishing
- chemical mechanical
- nitride film
- grinding
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- 239000000126 substance Substances 0.000 title claims abstract description 91
- 239000006185 dispersion Substances 0.000 title claims abstract description 90
- 238000005498 polishing Methods 0.000 title claims abstract description 83
- 238000000227 grinding Methods 0.000 title claims description 83
- 238000000034 method Methods 0.000 title claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- 239000008187 granular material Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 67
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 67
- 239000000758 substrate Substances 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000002296 dynamic light scattering Methods 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 108010001535 sulfhydryl oxidase Proteins 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 32
- 239000008119 colloidal silica Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- -1 metal ion Chemical class 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B13/00—Machines or devices designed for grinding or polishing optical surfaces on lenses or surfaces of similar shape on other work; Accessories therefor
- B24B13/015—Machines or devices designed for grinding or polishing optical surfaces on lenses or surfaces of similar shape on other work; Accessories therefor of television picture tube viewing panels, headlight reflectors or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/02—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents designed for particular workpieces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Aqueous dispersion for chemical mechanical polishing involved in the present invention, is characterized in that, has silicon dioxide granule and (B) acid compound of at least a kind of functional group be selected from sulfo group and salt thereof containing (A).
Description
Technical field
The present invention relates to aqueous dispersion for chemical mechanical polishing and utilize its chemical and mechanical grinding method.
Background technology
Actual conditions are in the past that can to reach the aqueous dispersion for chemical mechanical polishing of practical grinding rate in the cmp (hereinafter also referred to " CMP ") of silicon oxide layer, poly-silicon fiml very common, but then, the aqueous dispersion for chemical mechanical polishing that can reach the grinding rate of practicality in the CMP of silicon nitride film exists hardly.Due to such actual conditions, the method thus utilize and silicon nitride film formed barrier layer (ス ト ッ パ ー), being removed the silicon oxide layer formed on this silicon nitride film by CMP.Then, final needs also removes the silicon nitride film as barrier layer.
As the method for removing silicon nitride film, adopted in the past and utilize hot phosphoric acid to carry out the method for etch processes.But, because the method controls etch processes with the time, therefore, sometimes produce the residual film of silicon nitride film or damage caused to the lower floor of silicon nitride film.So, silicon nitride film is also wished to the method utilizing CMP to remove.
In order to utilize CMP optionally to remove silicon nitride film, must make to increase fully relative to the grinding rate ratio (hereinafter also referred to " Selection radio ") of the silicon nitride film of silicon oxide layer.Propose several aqueous dispersion for chemical mechanical polishing possessing such characteristic as shown below.
Such as, in Japanese Unexamined Patent Publication 11-176773 publication, disclose the method utilizing the lapping liquid containing the silica that phosphoric acid or phosphoric acid derivatives and particle diameter are below 10nm optionally to grind silicon nitride film.The method utilizing and containing phosphoric acid, nitric acid, hydrofluoric acid and lapping liquid pH being adjusted to 1 ~ 5, silicon nitride film is ground is disclosed in Japanese Unexamined Patent Publication 2004-214667 publication.Disclose in Japanese Unexamined Patent Publication 2006-120728 publication containing the acid additives suppressing etching action, can the lapping liquid of optionally polishing silicon nitride film.
Summary of the invention
But, in the above-mentioned aqueous dispersion for chemical mechanical polishing recorded in Japanese Unexamined Patent Publication 11-176773 publication and Japanese Unexamined Patent Publication 2004-214667 publication, although Selection radio is can gratifying level, storage stability is poor, therefore, be difficult to industrially utilize.
On the other hand, in the above-mentioned aqueous dispersion for chemical mechanical polishing recorded in Japanese Unexamined Patent Publication 2006-120728 publication, in order to reach practical grinding rate when the CMP of silicon nitride film, therefore this point of height grinding pressure of about 5psi is needed, in the pH region demonstrating high selectivity, the storage stability of lapping liquid is poor, therefore there is the problems such as the problem of storage life, the cut that caused by the abrasive particle condensed.
So several modes involved in the present invention provide by solving above-mentioned problem not need high grinding pressure, grinding rate relative to the silicon nitride film of silicon oxide layer can being made than increasing fully and the good aqueous dispersion for chemical mechanical polishing of storage stability and utilize its chemical and mechanical grinding method.
The present invention in order to solve carrying out at least partially of above-mentioned problem, can in the following manner or the form of Application Example realize.
[Application Example 1]
A mode of aqueous dispersion for chemical mechanical polishing involved in the present invention, is characterized in that, contain:
(A) there is the silicon dioxide granule of at least a kind of functional group be selected from sulfo group and salt thereof, and
(B) acid compound.
[Application Example 2]
In Application Example 1, above-mentioned (B) acid compound can be organic acid.
[Application Example 3]
In Application Example 1 or Application Example 2, pH can be 1 ~ 6.
[Application Example 4]
In Application Example 3, the electro kinetic potential of above-mentioned (A) silicon dioxide granule in aqueous dispersion for chemical mechanical polishing can be below-20mV.
[Application Example 5]
In arbitrary example in Application Example 1 ~ Application Example 4, when adopting dynamic light scattering determination, the average grain diameter of above-mentioned (A) silicon dioxide granule can be 15nm ~ 100nm.
[Application Example 6]
The aqueous dispersion for chemical mechanical polishing recorded in arbitrary example in Application Example 1 ~ Application Example 5 may be used for grind form semiconductor device polylith substrate among when cmp with the substrate of positive charge.
[Application Example 7]
In Application Example 6, the above-mentioned substrate with positive charge can be silicon nitride film.
[Application Example 8]
A mode of chemical and mechanical grinding method involved in the present invention, it is characterized in that, utilize the aqueous dispersion for chemical mechanical polishing recorded in arbitrary example in Application Example 1 ~ Application Example 7, the substrate when cmp with positive charge among the polylith substrate forming semiconductor device is ground.
With positive charge when among the known substrate forming semiconductor device, the surface of silicon nitride thing is at cmp, the surface of Si oxide when cmp with negative electrical charge.Therefore, utilize aqueous dispersion for chemical mechanical polishing involved in the present invention, because (A) has the surface of the silicon dioxide granule of at least a kind of functional group be selected from sulfo group and salt thereof with negative electrical charge, therefore, optionally can grind the substrate (such as, silicon nitride film) with positive charge when cmp.And then, by the synergy with (B) acid compound, grinding rate relative to the silicon nitride film of silicon oxide layer especially can be made than more increasing.
In addition, silicon nitride film is being formed barrier layer, is utilizing CMP silicon oxide layer to cave in such semiconductor device relative to silicon nitride film by aqueous dispersion for chemical mechanical polishing involved in the present invention, especially can play effect in the purposes of grinding removing silicon nitride film.
Accompanying drawing explanation
Fig. 1 be pattern represent the sectional view of the handled object of the use of the chemical and mechanical grinding method be suitable for involved by present embodiment.
Fig. 2 is the pattern ground sectional view of handled object when representing that the 1st grinding step completes.
Fig. 3 is the pattern ground sectional view of handled object when representing that the 2nd grinding step completes.
Fig. 4 be pattern represent the stereogram of chemical mechanical polishing device.
Fig. 5 is the sectional view that pattern earth's surface is shown in the handled object used in experimental example.
Fig. 6 be pattern represent the sectional view of the handled object of preparation when having ground.
Fig. 7 be pattern represent the sectional view of handled object when formally having ground.
Detailed description of the invention
Below, involved in the present invention is preferred embodiment described in detail.In addition, the present invention is not limited to following embodiment, is also included within the scope not changing purport of the present invention the various variation implemented.
1. aqueous dispersion for chemical mechanical polishing
Aqueous dispersion for chemical mechanical polishing involved by an embodiment of the invention is characterized in that, has silicon dioxide granule (hereinafter also referred to as " (A) silicon dioxide granule ") and (B) acid compound of at least a kind of functional group be selected from sulfo group and salt thereof containing (A).Below each composition contained by the aqueous dispersion for chemical mechanical polishing involved by present embodiment is described in detail.
1.1. (A) silicon dioxide granule
Aqueous dispersion for chemical mechanical polishing involved by present embodiment contains (A) and has the silicon dioxide granule of at least a kind of functional group be selected from sulfo group and salt thereof as abrasive particle.Namely, the silicon dioxide granule used in the present embodiment is the silicon dioxide granule at least a kind of functional group be selected from sulfo group and salt thereof be fixed on via covalent bond on its surface on surface, is not adsorbed on the such silicon dioxide granule in its surface with comprising the compound physical ground with at least a kind of functional group be selected from sulfo group and salt thereof or ion.In addition, in the present invention, so-called " salt of sulfo group " refers to the cation such as metal ion, ammonium ion replacement sulfo group (-SO
3h) hydrogen ion contained by and the functional group obtained.
The silicon dioxide granule used in the present embodiment can manufacture as follows.
First, silicon dioxide granule is prepared.As silicon dioxide granule, such as, can enumerate aerosil, colloidal silica etc., but from the viewpoint of grinding defects such as minimizing cuts, preferred colloidal silica.The colloidal silica that colloidal silica can use the known method by such as recording in Japanese Unexamined Patent Publication 2003-109921 publication etc. to manufacture.By modifying the surface of such silicon dioxide granule, the silicon dioxide granule that (A) that can use in the present embodiment has at least a kind of functional group be selected from sulfo group and salt thereof can be manufactured.Below exemplified with the method for modifying the surface of silicon dioxide granule, but the present invention is not subject to any restriction of this concrete example.
The modification of silica particle surface can be applied in Japanese Unexamined Patent Publication 2010-269985 publication, J.Ind.Eng.Chem., Vol.12, No.6, the known method recorded in (2006) 911-917 etc.Such as can by above-mentioned silicon dioxide granule and the silane coupler containing sulfydryl being stirred fully in acid medium, thus the silane coupler covalent bonding containing sulfydryl be realized on the surface of above-mentioned silicon dioxide granule.As the silane coupler containing sulfydryl, such as, can enumerate 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane etc.
Then, add hydrogen peroxide by appropriate further and fully places, the silicon dioxide granule with at least a kind of functional group be selected from sulfo group and salt thereof can be obtained.
(A) average grain diameter of silicon dioxide granule can adopt the aqueous dispersion for chemical mechanical polishing involved by dynamic light scattering determination present embodiment and obtain.In this situation, the average grain diameter of (A) silicon dioxide granule is preferably 15nm ~ 100nm, is more preferably 30nm ~ 70nm.If (A) average grain diameter of silicon dioxide granule is above-mentioned scope, then sometimes can reach practical grinding rate.And then the grinding rate of silicon oxide layer has the trend that can suppress.As the particle size determination device according to dynamic light scattering method, the nano particle analyzer " DelsaNanoS " of BeckmanCoulter Inc., " Zetasizernanozs " of Malvern Inc. etc. can be enumerated.In addition, the average grain diameter of dynamic light scattering determination is adopted to represent the average grain diameter of the offspring that the cohesion of multiple primary particle is formed.
When the pH of aqueous dispersion for chemical mechanical polishing is 1 ~ 6, the electro kinetic potential of (A) silicon dioxide granule is negative potential in aqueous dispersion for chemical mechanical polishing, and preferably its negative potential is below-20mV.If negative potential is below-20mV, then effectively prevented particle cohesion each other by interparticle electrostatic repulsion and the substrate that sometimes can optionally grind when cmp with positive charge.In addition, as electro kinetic potential determinator, " ELSZ-1 " of Otsuka Electronics Co., Ltd., " Zetasizernanozs " of Malvern Inc. etc. can be enumerated.(A) electro kinetic potential of silicon dioxide granule suitably can be adjusted by the addition increasing and decreasing the above-mentioned silane coupler containing sulfydryl.
Relative to the gross mass of aqueous dispersion for chemical mechanical polishing, the content of (A) silicon dioxide granule is preferably 1 quality % ~ 10 quality %, is more preferably 2 quality % ~ 8 quality %, is particularly preferably 3 quality % ~ 6 quality %.
1.2. (B) acid compound
Aqueous dispersion for chemical mechanical polishing involved by present embodiment contains (B) acid compound.As (B) acid compound, organic acid and inorganic acid can be enumerated.Therefore, the aqueous dispersion for chemical mechanical polishing involved by present embodiment can use at least a kind that is selected from organic acid and inorganic acid.(B) acid compound plays due to the synergy with (A) silicon dioxide granule the action effect especially making the grinding rate of silicon nitride film increase.
As organic acid, be not particularly limited, such as, can enumerate malonic acid, maleic acid, citric acid, malic acid, tartaric acid, oxalic acid, lactic acid etc. and their salt.
As inorganic acid, be not particularly limited, such as, can enumerate phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid etc. and their salt.
Above-mentioned illustrative (B) acid compound can be used alone a kind, also two or more can be combinationally used.
As (B) acid compound, in the purposes of polishing silicon nitride film, preferred organic acid, more preferably tartaric acid, malic acid, citric acid, particularly preferably tartaric acid.Above-mentioned illustrative tartaric acid, malic acid and citric acid have more than 2 carboxyls and more than 1 hydroxyl in molecule.Because this hydroxyl can form hydrogen bond with the nitrogen atom existed in silicon nitride film, therefore, the surface of silicon nitride film exists a large amount of above-mentioned illustrative organic acid.Thus, play etching action by the carboxyl in above-mentioned illustrative organic acid, the grinding rate of silicon nitride film can be made to increase.
As mentioned above, by using above-mentioned illustrative tartaric acid, malic acid, citric acid as (B) acid compound, the grinding rate for silicon nitride film can be made more to increase.
Relative to the gross mass of aqueous dispersion for chemical mechanical polishing, the content of (B) acid compound is preferably 0.1 quality % ~ 5 quality %, is more preferably 0.2 quality % ~ 1 quality %, is particularly preferably 0.2 quality % ~ 0.5 quality %.
1.3. decentralized medium
Aqueous dispersion for chemical mechanical polishing involved by present embodiment contains decentralized medium.As decentralized medium, the blending agent of water, water and alcohol, blending agent etc. containing water and organic solvent having a miscibility with water can be enumerated.Among these, preferably use the blending agent of water, water and alcohol, more preferably use water.
1.4. other additive
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can add the additives such as surfactant, water soluble polymer, corrosion inhibitor, pH adjusting agent further as required.Below, each additive is described.
1.4.1. surfactant
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can add surfactant further as required.Surfactant has the effect of the viscosity of aqueous dispersion for chemical mechanical polishing being given to appropriateness.The viscosity being preferably prepared into aqueous dispersion for chemical mechanical polishing at 25 DEG C for being more than or equal to 0.5mPas and being less than 10mPas.
As surfactant, be not particularly limited, anionic surfactant, cationic surfactant, nonionic surfactant etc. can be enumerated.
As anionic surfactant, such as, can enumerate the carboxylate such as fatty acid soaps, alkyl ether carboxy acid salt; The sulfonate such as alkylbenzenesulfonate, alkylnaphthalene sulfonate, alpha-alkene sulfonate; The sulfate such as higher alcohol sulfate salt, alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate salt; The phosphate ester salts such as alkyl phosphate; The fluorine-containing system such as all-fluoroalkyl compound surfactant etc.
As cationic surfactant, such as, can enumerate aliphatic amine salt, aliphatic ammonium salt etc.
As nonionic surfactant, such as, can enumerate the nonionic surfactant that acetylene series glycol, acetylene series glycol ethylene oxide adduct, acetylene alcohol etc. have triple bond; Polyethylene glycol type surfactant etc.In addition, also polyvinyl alcohol, cyclodextrin, polyvinyl methyl ether, hydroxyethylcellulose etc. can be used.
Among above-mentioned illustrative surfactant, preferred alkyl benzene sulfonate, more preferably Potassium dodecylbenzenesulfonate, DBSA ammonium.
These surfactants can be used alone a kind, also two or more can be combinationally used.
Relative to the gross mass of aqueous dispersion for chemical mechanical polishing, the content of surfactant is preferably 0.001 quality % ~ 5 quality %, is more preferably 0.01 quality % ~ 0.5 quality %, is particularly preferably 0.05 quality % ~ 0.2 quality %.
1.4.2. water soluble polymer
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can add water soluble polymer further as required.Water soluble polymer have be adsorbed on silicon nitride film surface on and the effect that abrasion friction is reduced.By this effect, silicon nitride film can be reduced and cave in.
As water soluble polymer, polyacrylamide, polyacrylic acid, polyvinyl alcohol, PVP, hydroxyethylcellulose etc. can be enumerated.
The content of water soluble polymer can be adjusted to the viscosity of aqueous dispersion for chemical mechanical polishing lower than 10mPas.
1.4.3. corrosion inhibitor
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can add corrosion inhibitor further as required.As corrosion inhibitor, such as, can enumerate BTA and derivative thereof.At this, so-called benzotriazole derivatives refers to that more than 1 or 2 hydrogen atom such as carboxyl, methyl, amino, the hydroxyl etc. had by BTA carry out replacing and the compound that obtains.As benzotriazole derivatives, 4-carboxyl benzotriazole and salt, 7-carboxyl benzotriazole and salt thereof, BTA butyl ester, 1-hydroxymethyl BTA or I-hydroxybenzotriazole etc. can be enumerated.
Relative to the gross mass of aqueous dispersion for chemical mechanical polishing, the addition of corrosion inhibitor is preferably below 1 quality %, is more preferably 0.001 quality % ~ 0.1 quality %.
1.4.4.pH conditioning agent
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can add pH adjusting agent further as required.As pH adjusting agent, such as, can enumerate the alkali compounds such as potassium hydroxide, ethylenediamine, TMAH (TMAH), ammonia.Aqueous dispersion for chemical mechanical polishing involved by present embodiment containing (B) acid compound, therefore, can utilize above-mentioned illustrative alkali compounds to carry out the adjustment of pH as described above usually.
1.5.pH
The pH of the aqueous dispersion for chemical mechanical polishing involved by present embodiment is not particularly limited, but is preferably 1 ~ 6, is more preferably 2 ~ 4.If pH is in above-mentioned scope, then the grinding rate of silicon nitride film can be made more to increase, on the other hand, the grinding rate of silicon oxide layer can be made more to reduce.Its result can selectively polishing silicon nitride film.And then if pH is 2 ~ 4, then the storage stability of aqueous dispersion for chemical mechanical polishing is good, thus more preferably.
1.6. purposes
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can use as the grinding material for grinding the substrate when cmp with positive charge among the polylith substrate of main composition semiconductor device.As the representative substrate when cmp with positive charge, the poly-silicon etc. of silicon nitride film, doping can be enumerated.Aqueous dispersion for chemical mechanical polishing involved by present embodiment is particularly suited for the purposes of polishing silicon nitride film among these.
In addition, the grinding rate ratio of the silicon nitride film relative to silicon oxide layer for the aqueous dispersion for chemical mechanical polishing involved by present embodiment can be said, under identical grinding condition when each self-grind silicon oxide layer, silicon nitride film, preferably the value of [grinding rate of the grinding rate/silicon oxide layer of silicon nitride film] is more than 3, is more preferably more than 4.
1.7. the preparation method of aqueous dispersion for chemical mechanical polishing
Aqueous dispersion for chemical mechanical polishing involved by present embodiment can by making above-mentioned each component dissolves or be dispersed in the decentralized media such as water to prepare.The method making it dissolve or to disperse is not particularly limited, as long as can dissolve equably or disperse, then any method all can be applied.In addition, the order by merging of above-mentioned each composition, mixed method are also not particularly limited.
In addition, the aqueous dispersion for chemical mechanical polishing involved by present embodiment also can be prepared into the stoste of concentrated type, and carries out diluting with decentralized media such as water in use and use.
2. chemical and mechanical grinding method
Chemical and mechanical grinding method involved by present embodiment is characterized in that, the aqueous dispersion for chemical mechanical polishing involved by the invention described above is utilized to grind the substrate (such as, silicon nitride film) when cmp with positive charge among the polylith substrate forming semiconductor device.Below, accompanying drawing is utilized to be described in detail the chemical and mechanical grinding method involved by present embodiment concrete example.
2.1. handled object
Fig. 1 be pattern represent the sectional view of the handled object of the use of the chemical and mechanical grinding method be suitable for involved by present embodiment.Handled object 100 can be formed through following operation (1) ~ (4).
(1) first, prepared silicon substrate 10.Silicon substrate 10 can be formed the function devices such as (not illustrating) transistor.
(2) then, CVD or thermal oxidation method is adopted to form the 1st silicon oxide film 12 on silicon substrate 10.Further employing CVD forms silicon nitride film 14 on the 1st silicon oxide layer 12.
(3) then, by silicon nitride film 14 patterning.It can be used as mask, application photoetching process or etching method form raceway groove 20.
(4) then, adopt high-density plasma CVD method to make the 2nd silicon oxide layer 16 pile up to fill raceway groove 20, thus obtain handled object 100.
2.2. chemical and mechanical grinding method
2.2.1. the 1st grinding step
First, in order to remove be deposited in the handled object 100 shown in Fig. 1 silicon nitride film 14 on the 2nd silicon oxide layer 16, utilize the aqueous dispersion for chemical mechanical polishing that the Selection radio of silicon oxide layer is large to carry out the 1st grinding step.Fig. 2 is the pattern ground sectional view of handled object when representing that the 1st grinding step completes.In the 1st grinding step, silicon nitride film 14 forms barrier layer, can stop grinding on the surface of silicon nitride film 14.Now, in the raceway groove 20 being filled with silica, depression is produced.Thus, as shown in Figure 2, remaining silicon nitride film 14, but on silicon nitride film 14, usually remain the grinding residue of the 2nd silicon oxide layer 16.This grinding residue impacts the grinding of silicon nitride film 14 afterwards sometimes.
2.2.2. the 2nd grinding step
Then, in order to remove the silicon nitride film 14 shown in Fig. 2, the aqueous dispersion for chemical mechanical polishing involved by above-mentioned present embodiment is utilized to carry out the 2nd grinding step.Fig. 3 is the pattern ground sectional view of handled object when representing that the 2nd grinding step completes.For the aqueous dispersion for chemical mechanical polishing involved by present embodiment, because the grinding rate of the silicon nitride film relative to silicon oxide layer is large fully, the grinding rate of silicon oxide layer is not low terrifically, so the impact of the grinding residue of silicon oxide layer can not be subject to, successfully grinding removing silicon nitride film 14.The semiconductor device embedding silica in raceway groove 20 shown in Fig. 3 can be obtained like this.Chemical and mechanical grinding method involved by present embodiment may be used for such as raceway groove and is separated (STI) etc.
2.3. chemical mechanical polishing device
Can example chemical mechanical polishing device 200 as shown in Figure 4 in above-mentioned 1st grinding step and the 2nd grinding step.Fig. 4 be pattern represent the stereogram of chemical mechanical polishing device 200.Each grinding step carries out in the following way: supply slurry (aqueous dispersion for chemical mechanical polishing) 44 by slurry supply nozzle 42 and the turntable 48 being pasted with abrasive cloth 46 is rotated, while make the holder head (carrierhead) 52 of maintenance semiconductor substrate 50 abut.In addition, water supply nozzle 54 and trimmer 56 is also shown in the lump in the diagram.
The pushing force of holder head 52 can be selected in the scope of 10 ~ 1,000hPa, is preferably 30 ~ 500hPa.In addition, the rotating speed of turntable 48 and holder head 52 suitably can be selected in the scope of 10 ~ 400rpm, is preferably 30 ~ 150rpm.The flow of the slurry (aqueous dispersion for chemical mechanical polishing) 44 supplied by slurry supply nozzle 42 can be selected in the scope of 10 ~ 1,000mL/ minute, is preferably 50 ~ 400mL/ minute.
As commercially available lapping device, such as, can enumerate the model " EPO-112 " of Ebara Corporation, " EPO-222 "; The model " LGP-510 " of LapmasterSFT Inc., " LGP-552 "; The model " Mirra ", " Reflexion " etc. of AppliedMaterial Inc..
3. embodiment
, by embodiment, the present invention is described below, but the present invention is not limited to these embodiments.
The preparation of the aqueous dispersion 3.1. containing colloidal silica
Be 2000cm at capacity
3flask in add ammoniacal liquor 70g, ion exchange water 40g, the ethanol 175g and tetraethoxysilane 21g of 25 quality % concentration, while stir limit to be warmed up to 60 DEG C under 180rpm.Keep 60 DEG C to stir cooling after 1 hour, thus obtain colloidal silica/alcohol dispersion.Then, utilize evaporimeter, carry out the operation that ion-exchange waterside removing alkoxide component is added on limit at 80 DEG C in this dispersion, this operation is repeated for several times, thus the alcohol in removing dispersion, prepare the aqueous dispersion that solid component concentration is 15%.The sample obtained is diluted for the part ion exchange water taking out this aqueous dispersion, utilize dynamic light scattering formula particle size determination device (Horiba Ltd's system, model " LB550 ") measure average diameter as average grain diameter, result is 35nm.
The colloidal silica aqueous dispersion of other average grain diameter (10nm, 50nm, 70nm, 130nm) is by adopting the method identical with said method suitably to adjust the addition of tetraethoxysilane and mixing time makes.
In addition, in table, the aqueous dispersion usually containing colloidal silica obtained in a manner described is called " silicon dioxide types B ".
3.2. the preparation of the aqueous dispersion of colloidal silica is modified containing sulfo group
In ion exchange water 50g, add acetic acid 5g, drip silane coupler (Shin-Etsu Chemial Co., Ltd's system, trade name " the KBE803 ") 5g containing sulfydryl while stirring further lentamente.After 30 minutes, be added on the aqueous dispersion 1000g of preparation in " preparation that 3.1. contains the aqueous dispersion of colloidal silica ", continue stirring 1 hour further.Afterwards, add 31% aquae hydrogenii dioxidi 200g, at room temperature place 48 hours, obtain the colloidal silica with at least a kind of functional group be selected from sulfo group and salt thereof thus.The sample obtained is diluted for the part ion exchange water taking out this aqueous dispersion, utilize dynamic light scattering formula particle size determination device (Horiba Ltd's system, model " LB550 ") measure average diameter as average grain diameter, result is 35nm.
For the colloidal silica aqueous dispersion of other average grain diameter (10nm, 50nm, 70nm, 130nm), the surface of colloidal silica also can be modified by sulfo group in the same manner as said method.The average grain diameter of sulfo group other than the above being modified to colloidal silica aqueous dispersion also measures in the same manner as said method, and result can not confirm the increase and decrease of average grain diameter.
In addition, in table, the aqueous dispersion containing sulfo group modification colloidal silica obtained in a manner described is called " silicon dioxide types A ".
3.3. the preparation of aqueous dispersion for chemical mechanical polishing
It is 1000cm that the aqueous dispersion prepared in " 3.2. contains the preparation that sulfo group modifies the aqueous dispersion of colloidal silica " of ormal weight is joined capacity
3polyethylene bottle in, add in the mode reaching the content that token carries the acidic materials that token carries wherein respectively, and fully to stir.Afterwards, add ion exchange water while stirring, after being adjusted to the silica concentration of regulation, use ammonia to be the pH of the regulation recorded in table further.Afterwards, be the metre filter of 5 μm with aperture, thus obtain the aqueous dispersion for chemical mechanical polishing of embodiment 1 ~ 10 and comparative example 1 ~ 5.
For the aqueous dispersion for chemical mechanical polishing obtained, utilize electro kinetic potential determinator (Otsuka Electronics Co., Ltd. system, model " ELSZ-1 ") measure the electro kinetic potential that sulfo group modifies colloidal silica.Be the results are shown in table 1 and table 2.
3.4. cmp test
Utilize the aqueous dispersion for chemical mechanical polishing of preparation in " preparation of 3.3. aqueous dispersion for chemical mechanical polishing ", using with diameter be the silicon nitride film of 8 inches or the silicon substrate of silicon oxide layer as polished body, 1 time cmp is carried out to respective film at following grinding condition.
< grinding condition 1 >
Lapping device: Ebara Corporation's system, model " EPO-112 "
Grinding pad: RodelNitta Co., Ltd. system, " IC1000/K-Groove "
Aqueous dispersion for chemical mechanical polishing feed speed: 200mL/ minute
Platform rotating speed: 90rpm
Grinding head rotating speed: 90rpm
Grinding head pushing force: 140hPa
3.4.1. the calculating of grinding rate
Be the silicon nitride film of 8 inch or the substrate of silicon oxide layer as polished body with diameter to each, thickness before utilizing the light interference type film thickness gauge " NanoSpec6100 " of NANOMETRICSJAPAN Co., Ltd. to measure grinding in advance, carries out grinding in 1 minute under these conditions.Light interference type film thickness gauge is similarly utilized to measure the thickness of the polished body after grinding, and the film thickness difference before trying to achieve grinding and after grinding, the thickness namely reduced by cmp.Then, the thickness reduced by cmp and milling time calculate grinding rate.This be the results are shown in table 1 ~ 2.
3.4.2. the evaluation of storage stability
The aqueous dispersion for chemical mechanical polishing made in " preparation of 3.3. aqueous dispersion for chemical mechanical polishing " item of 500cc is added in the plastic bottle (Port リ bottle) of 500cc, store 2 weeks under the environment of 25 DEG C.For the change of storage forward backward averaging particle diameter, dynamic light scattering formula particle size determination device (Horiba Ltd's system, model " LB550 ") is utilized to measure average diameter as average grain diameter.For the particle diameter before storage, the increase of average grain diameter after release from storage judges into storage stability very well as " ◎ " when being less than 5%, judging into good when being more than or equal to 5% and being less than 10% is "○", judges into and differ from as "×" and being recorded in table when being more than or equal to 10%.
3.4.3. evaluation result
In embodiment 1 ~ 10, be raised to more than 3 relative to the grinding rate of the silicon nitride film of silicon oxide layer.
Comparative example 1 uses sulfo group to modify colloidal silica but do not contain the example of acidic materials.In this case, grinding rate, than not enough, can not be applied.
Comparative example 2 ~ 4 is the examples using common colloidal silica, change acidic materials kind.In arbitrary comparative example, be grinding rate relative to the silicon nitride film of silicon oxide layer than little, storage stability is poor, thus can not apply.
Comparative example 5 is the use of the example of the little common colloidal silica of average grain diameter.Although grinding rate is than improving, grinding rate is too small, and storage stability is poor, thus can not apply.
[table 1]
[table 2]
3.5. experimental example
Cmp is carried out with the test wafer being pre-embedded with silicon nitride film.Specifically, as handled object 300,864CMP is adopted (to be the test wafer of AdvancedMaterialsTechnology Inc., there is the cross section structure shown in Fig. 5, obtain as follows: after making the 1st silicon oxide layer 112, silicon nitride film 114 pile up successively on naked silicon 110, utilize lithography process to carry out ditch processing, adopt high-density plasma CVD method to make the 2nd silicon oxide layer 116 pile up and obtain wafer further).
Above-mentioned test wafer uses CMS4301 and CMS4302 of JSR Corp. to carry out preparation grinding for 2 times until the upper surface of silicon nitride film 114 exposes at following grinding condition in advance.Exposing of silicon nitride film 114 is flowed by utilizing endpoint detector to detect the workbench torque current (テ ー Block Le ト Le Network Electricity of grinder) change confirm.
< grinding condition 2 >
Lapping device: Ebara Corporation's system, model " EPO-112 "
Grinding pad: RodelNitta Co., Ltd. system, " IC1000/K-Groove "
Aqueous dispersion for chemical mechanical polishing feed speed: 200mL/ minute
Platform rotating speed: 100rpm
Holder head rotating speed: 110rpm
Bearing pushing force: 210hPa
Fig. 6 be pattern represent the sectional view of handled object (864CMP) state after preparation grinding.As shown in Figure 6, the polished face after cmp completely removes the 2nd silicon oxide layer 116 formed on silicon nitride film 114.Utilize light interference type film thickness gauge " NanoSpec6100 " to measure the thickness of the silicon nitride film 114 in 100 μm of spacing of pattern density 50%, the thickness of result silicon nitride film 114 is about 150nm.
In addition, utilize contact pin type drop determinator " HRP240 " mensuration relative to the cup depth of the 2nd silicon oxide layer 116 of silicon nitride film 114, result cup depth is about 40nm.
Finally, the aqueous dispersion for chemical mechanical polishing used in embodiment 1 is used to carry out for 1 time formally grinding for 150 seconds at above-mentioned grinding condition.Fig. 7 be pattern represent the sectional view of handled object (864CMP) state after formal grinding.
As shown in Figure 7, the thickness of the silicon nitride film 114 after formal grinding in polished face is roughly 0nm.Cup depth in 100 μm of spacing of known pattern density 50% is about 20nm, is preferred in expectation element separating property.
As known from the above, the grinding rate of the silicon nitride film relative to silicon oxide layer of the aqueous dispersion for chemical mechanical polishing involved by present embodiment than large fully, optionally polishing silicon nitride film in the semiconductor device that can coexist at silicon oxide layer and silicon nitride film.
Symbol description
10110 ... silicon substrate (naked silicon), 12112 ... 1st silicon oxide layer, 14114 ... silicon nitride film, 16116 ... 2nd silicon oxide layer, 20 ... raceway groove, 42 ... slurry supply nozzle, 44 ... slurry, 46 ... abrasive cloth, 48 ... turntable, 50 ... semiconductor substrate, 52 ... holder head, 54 ... water supply nozzle, 56 ... trimmer, 100200 ... handled object, 300 ... chemical mechanical polishing device.
Claims (8)
1. an aqueous dispersion for chemical mechanical polishing, contains:
A silicon dioxide granule, and
B acid compound,
Wherein, described A silicon dioxide granule is, by make the surface of silicon dioxide granule with containing after the silane coupler covalent bond of sulfydryl, make described sulfhydryl oxidase, at least a kind of functional group be selected from sulfo group and salt thereof fixed silicon dioxide granule in its surface on its surface via covalent bond.
2. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, described B acid compound is organic acid.
3. aqueous dispersion for chemical mechanical polishing according to claim 1 and 2, wherein, pH is 1 ~ 6.
4. aqueous dispersion for chemical mechanical polishing according to claim 3, wherein, the electro kinetic potential of the described A silicon dioxide granule in aqueous dispersion for chemical mechanical polishing is below-20mV.
5. aqueous dispersion for chemical mechanical polishing according to claim 1 and 2, wherein, when adopting dynamic light scattering determination, the average grain diameter of described A silicon dioxide granule is 15nm ~ 100nm.
6. aqueous dispersion for chemical mechanical polishing according to claim 1 and 2, its for grind form semiconductor device polylith substrate among when cmp with the substrate of positive charge.
7. aqueous dispersion for chemical mechanical polishing according to claim 6, wherein, the described substrate with positive charge is silicon nitride film.
8. a chemical and mechanical grinding method, it is characterized in that, utilize the aqueous dispersion for chemical mechanical polishing according to any one of claim 1 ~ 7 to grind the substrate when cmp with positive charge among the polylith substrate forming semiconductor device.
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| JP2010-020109 | 2010-02-01 | ||
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| PCT/JP2011/050624 WO2011093153A1 (en) | 2010-02-01 | 2011-01-17 | Aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method using same |
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| JP5695367B2 (en) * | 2010-08-23 | 2015-04-01 | 株式会社フジミインコーポレーテッド | Polishing composition and polishing method using the same |
| JP5927806B2 (en) * | 2011-08-16 | 2016-06-01 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion and chemical mechanical polishing method using the same |
| JP5907333B2 (en) * | 2011-08-22 | 2016-04-26 | Jsr株式会社 | Chemical mechanical polishing aqueous dispersion and chemical mechanical polishing method using the same |
| JP2013138053A (en) * | 2011-12-28 | 2013-07-11 | Fujimi Inc | Polishing composition |
| JP5957292B2 (en) * | 2012-05-18 | 2016-07-27 | 株式会社フジミインコーポレーテッド | Polishing composition, polishing method using the same, and substrate manufacturing method |
| JP6054149B2 (en) * | 2012-11-15 | 2016-12-27 | 株式会社フジミインコーポレーテッド | Polishing composition |
| JP6057706B2 (en) * | 2012-12-28 | 2017-01-11 | 株式会社フジミインコーポレーテッド | Polishing composition |
| KR20150113956A (en) * | 2013-02-01 | 2015-10-08 | 가부시키가이샤 후지미인코퍼레이티드 | Surface selective polishing compositions |
| KR20160002729A (en) * | 2013-04-25 | 2016-01-08 | 히타치가세이가부시끼가이샤 | Cmp polishing solution and polishing method using same |
| KR20160009579A (en) * | 2013-05-15 | 2016-01-26 | 바스프 에스이 | Chemical-mechanical polishing compositions comprising one or more polymers selected from the group consisting of n-vinyl-homopolymers and n-vinyl copolymers |
| JP2016524326A (en) * | 2013-05-15 | 2016-08-12 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Chemical mechanical polishing composition comprising N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylenediamine or methanesulfonic acid |
| WO2014184708A2 (en) * | 2013-05-15 | 2014-11-20 | Basf Se | Use of a chemical-mechanical polishing (cmp) composition for polishing a substrate or layer containing at least one iii-v material |
| MY178806A (en) | 2013-05-15 | 2020-10-20 | Basf Se | Chemical-mechanical polishing compositions comprising polyethylene imine |
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| KR20120134105A (en) | 2012-12-11 |
| EP2533274A4 (en) | 2013-06-26 |
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| SG182790A1 (en) | 2012-09-27 |
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| TW201139634A (en) | 2011-11-16 |
| EP2533274A1 (en) | 2012-12-12 |
| JP5915843B2 (en) | 2016-05-11 |
| CN102741985A (en) | 2012-10-17 |
| WO2011093153A1 (en) | 2011-08-04 |
| EP2533274B1 (en) | 2014-07-30 |
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